EP0130439A1 - Process for the preparation of vinylphosphonic acid or vinylpyrophonic acid - Google Patents
Process for the preparation of vinylphosphonic acid or vinylpyrophonic acid Download PDFInfo
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- EP0130439A1 EP0130439A1 EP84106863A EP84106863A EP0130439A1 EP 0130439 A1 EP0130439 A1 EP 0130439A1 EP 84106863 A EP84106863 A EP 84106863A EP 84106863 A EP84106863 A EP 84106863A EP 0130439 A1 EP0130439 A1 EP 0130439A1
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- acid
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- phosphorus trichloride
- phosphorous acid
- water
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 4
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 title description 6
- 239000002253 acid Substances 0.000 title description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000002576 ketones Chemical class 0.000 claims abstract description 18
- -1 vinyl pyrophosphonic acid Chemical compound 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000012442 inert solvent Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N phosphorus trioxide Inorganic materials O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- NAISYYJIARZUIC-UHFFFAOYSA-N 3,4-dihydronaphthalen-1-ylphosphonic acid Chemical compound C1=CC=C2C(P(O)(=O)O)=CCCC2=C1 NAISYYJIARZUIC-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- LVEKJWLAJJVWIT-UHFFFAOYSA-N cyclohexen-1-ylphosphonic acid Chemical compound OP(O)(=O)C1=CCCCC1 LVEKJWLAJJVWIT-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YOKDQEBPBYOXHX-UHFFFAOYSA-N prop-1-en-2-ylphosphonic acid Chemical compound CC(=C)P(O)(O)=O YOKDQEBPBYOXHX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3826—Acyclic unsaturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/383—Cycloaliphatic acids
Definitions
- the present invention relates to a process for the preparation of derivatives of vinylphosphonic or vinyl pyrophosphonic acid by reacting ketones with phosphorus trichloride at elevated temperatures.
- Vinylphosphonic acid and its derivatives are of technical interest because they polymerize to high molecular weight compounds or can be processed with other polymerizable compounds to form a copolymer.
- 1-phenylvinyl-1-phosphonic acid or its homopolymer or copolymers with other vinyl compounds are used for the aftertreatment of phosphated metal surfaces (DE-OS 24 55 624, DE-OS 26 15 489).
- the new process is characterized in that a ketone is reacted with phosphorous acid and phosphorus trichloride in a molar ratio of 2: 1: 1, if appropriate in an inert solvent at temperatures between 20 and 150 ° C, in particular between 40 - 120 ° C, wherein 1 mole of phosphorous acid can be replaced by a further mole of phosphorus trichloride and three equivalents of water, so that a total of 1 mole of phosphorus trichloride is added to a mixture of ketone and water in a molar ratio of 1: 1.5.
- the ketone is preferably initially introduced together with the phosphorous acid, heated to the reaction temperature and the phosphorus trichloride is metered in slowly, with hydrogen chloride escaping.
- ketone in excess, either in order to use it simultaneously as a solvent or in order to keep the residues of excess phosphorous acid in the end product low.
- a further possible variant of the process according to the invention consists in introducing the ketone together with the phosphorus trichloride in a molar ratio greater than or equal to one to one, if appropriate with the inert solvent, and then adding the water, analogously requiring 1.5 equivalents of water.
- half of the phosphorus trichloride and the water can also be replaced by the corresponding amount of phosphoric acid.
- a thermal aftertreatment of the initially obtained crude product follows before or after the hydrolysis.
- the reaction product is heated to temperatures between the reaction temperature and 250 ° C. for 1 to 60 minutes.
- the respective minimum temperature depends on the reactivity of the ketone used.
- R and R ' can be identical or different and represent hydrogen or a halogen-substituted or unsubstituted alkyl, aryl, alkaryl or aralkyl radical having 1 to 18 carbon atoms, while R "is an alkyl, aryl -, Alkaryl or aralkyl radical having 1 to 18 carbon atoms.
- 1- (4-bromophenyl) vinyl-1-phosphonic acid crystallizes from the solution in colorless crystals. 85 g (0.32 mol) of the phosphonic acid are isolated, which corresponds to a yield of 80.8%. The yield can be further increased by recirculating the mother liquor.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Derivaten der Vinylphosphon-, oder Vinylpyrophosphonsäure durch Umsetzung von Ketonen mit Phosphortrichlorid, indem man Keton und phosphorige Säure zusammen mit Phosphortrichlorid in einem Molverhältnis von 2 : 1 : 1 umsetzt, wobei gegebenenfalls 1 Mol phosphorige Säure durch ein weiteres Mol Phosphortrichlorid und 3 Mol Wasser ersetzt werden kann.The present invention relates to a process for the preparation of derivatives of vinylphosphonic or vinyl pyrophosphonic acid by reacting ketones with phosphorus trichloride by reacting ketone and phosphorous acid together with phosphorus trichloride in a molar ratio of 2: 1: 1, optionally 1 mol of phosphorous acid another mole of phosphorus trichloride and 3 moles of water can be replaced.
Description
Gegenstand vorliegender Erfindung ist ein Verfahren zur Herstellung von Derivaten der Vinylphosphon-, oder Vinylpyrophosphonsäure durch Umsetzung von Ketonen mit Phosphortrichlorid bei erhöhten Temperaturen.The present invention relates to a process for the preparation of derivatives of vinylphosphonic or vinyl pyrophosphonic acid by reacting ketones with phosphorus trichloride at elevated temperatures.
Vinylphosphonsäure und ihre Derivate sind von technischem Interesse, da sie zu hochmolekularen Verbindungen polymerisieren oder mit anderen polymerisationsfähigen Verbindungen zu einem Mischpolymerisat verarbeitet werden können.Vinylphosphonic acid and its derivatives are of technical interest because they polymerize to high molecular weight compounds or can be processed with other polymerizable compounds to form a copolymer.
Beispielsweise werden 1-Phenylvinyl-1-phosphonsäure bzw. ihr Homopolymer oder Copolymere mit anderen Vinyl-Verbindungen zur Nachbehandlung phosphatierter Metalloberflächen verwendet (DE-OS 24 55 624, DE-OS 26 15 489).For example, 1-phenylvinyl-1-phosphonic acid or its homopolymer or copolymers with other vinyl compounds are used for the aftertreatment of phosphated metal surfaces (DE-OS 24 55 624, DE-OS 26 15 489).
Stand der Technik zur Herstellung von substituierten Vinylphosphonsäuren ist ein Verfahren, bei dem ein Keton mit Phosphortrichlorid in Gegenwart von Eisessig zur Reaktion gebracht wird (Houben-Weyl, Methoden der organischen Chemie XII/1, 363-4 /79637). Unter Abspaltung von Acetylchlorid und Hydrogenchlorid entsteht dabei vermutlich eine cyclische Phosphonsäure, deren Hydrolyse 1-Hydroxyalkan-l-phosphonsäuren als Zwischenprodukte liefert, deren Dehydratisation durch Erhitzen in inerten Lösungsmitteln wie 1,1,2,2-Tetrachlorethan schließlich die gewünschte substituierte Vinylphosphonsäure liefert (DE-OS 20 60 218).State of the art for the production of substituted vinylphosphonic acids is a process in which a ketone is reacted with phosphorus trichloride in the presence of glacial acetic acid (Houben-Weyl, Methods of Organic Chemistry XII / 1, 363-4 / 79637). With the splitting off of acetyl chloride and hydrogen chloride, a cyclic phosphonic acid is presumably formed, the hydrolysis of which gives 1-hydroxyalkane-1-phosphonic acids as intermediates, the dehydration of which finally gives the desired substituted vinylphosphonic acid by heating in inert solvents such as 1,1,2,2-tetrachloroethane ( DE-OS 20 60 218).
Diese, über mehrere Zwischenstufen verlaufende Arbeitsweise ist jedoch sehr aufwendig.However, this procedure, which runs over several intermediate stages, is very complex.
Überraschenderweise wurde nun gefunden, daß ein wesentlich einfacherer Zugang zu Derivaten der Vinylphosphonsäure möglich ist, wenn man im oben genannten Verfahren den Eisessig durch phosphorige Säure ersetzt.Surprisingly, it has now been found that a much easier access to derivatives of vinylphosphonic acid is possible if the glacial acetic acid is replaced by phosphorous acid in the process mentioned above.
Das neue Verfahren ist dadurch gekennzeichnet, daß man ein Keton mit phosphoriger Säure und Phosphortrichlorid im Molverhältnis 2 : 1 : 1,gegebenenfalls in einem inerten Lösemittel bei Temperaturen zwischen 20 und 150°C, insbesondere zwischen 40 - 120°C,zur Reaktion bringt, wobei 1 Mol phosphorige Säure durch ein weiteres Mol Phosphortrichlorid und drei Äquivalente Wasser ersetzt werden kann, so daß zu einer Mischung von Keton und Wasser im Molverhältnis 1 : 1,5 insgesamt 1 Mol Phosphortrichlorid zugesetzt wird. Vorzugsweise wird das Keton zusammen mit der phosphorigen Säure vorgelegt, auf die Reaktionstemperatur erhitzt und das Phosphortrichlorid langsam zudosiert, wobei Hydrogenchlorid entweicht.The new process is characterized in that a ketone is reacted with phosphorous acid and phosphorus trichloride in a molar ratio of 2: 1: 1, if appropriate in an inert solvent at temperatures between 20 and 150 ° C, in particular between 40 - 120 ° C, wherein 1 mole of phosphorous acid can be replaced by a further mole of phosphorus trichloride and three equivalents of water, so that a total of 1 mole of phosphorus trichloride is added to a mixture of ketone and water in a molar ratio of 1: 1.5. The ketone is preferably initially introduced together with the phosphorous acid, heated to the reaction temperature and the phosphorus trichloride is metered in slowly, with hydrogen chloride escaping.
Vorteilhaft kann es außerdem sein, das Keton im Überschuß einzusetzen, entweder um es gleichzeitig als Lösemittel zu verwenden oder um die Reste von überschüssiger phosphoriger Säure im Endprodukt gering zu halten.It may also be advantageous to use the ketone in excess, either in order to use it simultaneously as a solvent or in order to keep the residues of excess phosphorous acid in the end product low.
Eine weitere mögliche Variante des erfindungsgemäßen Verfahrens besteht darin, das Keton zusammen mit dem Phosphortrichlorid im Molverhältnis größer gleich eins zu eins, gegebenenfalls mit dem inerten Lösemittel, vorzulegen und dann das Wasser zuzusetzen, wobei analog 1,5 Äquivalente Wasser benötigt werden. Natürlich kann auch hier die Hälfte des Phosphortrichlorids und das Wasser durch die entsprechende Stoffmenge phosphoriger Säure ersetzt werden.A further possible variant of the process according to the invention consists in introducing the ketone together with the phosphorus trichloride in a molar ratio greater than or equal to one to one, if appropriate with the inert solvent, and then adding the water, analogously requiring 1.5 equivalents of water. Of course, half of the phosphorus trichloride and the water can also be replaced by the corresponding amount of phosphoric acid.
Im Falle reaktiver Ketone, wie z.B. Acetophenon, werden in erster Linie Vinylpyrophosphonsäuren gebildet, die - sofern gewünscht - mit stöchiometrischen Wassermengen in bekannter Weise zu den entsprechenden Vinylphosphonsäuren hydrolysiert werden können.In the case of reactive ketones, e.g. Acetophenone, primarily vinyl pyrophosphonic acids are formed, which - if desired - can be hydrolyzed with stoichiometric amounts of water in a known manner to the corresponding vinyl phosphonic acids.
Im Falle wenig reaktiver Ketone schließt sich vor oder nach der Hydrolyse eine thermische Nachbehandlung des zunächst anfallenden Rohprodukts an. Dazu wird das Reaktionsprodukt für 1 bis 60 Minuten auf Temperaturen zwischen der Umsetzungstemperatur und 250°C erhitzt. Die jeweilige Mindesttemperatur ist dabei von der Reaktionsfähigkeit des verwendeten Ketons abhängig. Als Keton kann eine Verbindung der allgemeinen Formel
eingesetzt werden, in der R und R' gleich oder verschieden sein können und für Wasserstoff oder einen halogensubstituierten oder nicht substituierten Alkyl-, Aryl-, Alkaryl-oder Aralkylrest mit 1 bis 18 C-Atomen stehen, während R" einen Alkyl-, Aryl-, Alkaryl- oder Aralkylrest mit 1 bis 18 C-Atomen darstellt.are used in which R and R 'can be identical or different and represent hydrogen or a halogen-substituted or unsubstituted alkyl, aryl, alkaryl or aralkyl radical having 1 to 18 carbon atoms, while R "is an alkyl, aryl -, Alkaryl or aralkyl radical having 1 to 18 carbon atoms.
Das neue Verfahren war für den Fachmann nicht vorhersehbar und besitzt gegenüber dem herkömmlichen, dem Stand der Technik entsprechenden Verfahren, u.a. den Vorteil, daß es nicht notwendig ist, einen Hilfsstoff wie Essigsäure zuzusetzen, so daß der Zwangsanfall eines Nebenproduktes wie Acetylchlorid vermieden wird. Es ist schon vorgeschlagen worden (DE-OS 31 25 329) Derivate der Vinylphosphon- oder Vinylpyrophosphonsäuren durch Umsetzung eines Ketons mit Tetraphosphorhexoxid in Gegenwart von katalytischen Mengen einer protonenabgebenden Substanz, wie z.B. H3P03, herzustellen, doch hat diese Arbeitsweise den Nachteil, daß sie sich nicht im technischen Maßstab durchführen läßt, da Tetraphosphorhexoxid kein technisches Produkt darstellt, nur im Labor arbeits- und kostenintensiv hergestellt werden kann und im allgemeinen mit elementarem gelben Phosphor verunreinigt ist.The new process was not foreseeable by the person skilled in the art and has compared to the conventional process which corresponds to the prior art, i.a. the advantage that it is not necessary to add an auxiliary such as acetic acid, so that the inevitable occurrence of a by-product such as acetyl chloride is avoided. It has already been proposed (DE-OS 31 25 329) derivatives of vinylphosphonic or vinylpyrophosphonic acids by reacting a ketone with tetraphosphorus hexoxide in the presence of catalytic amounts of a proton donating substance, e.g. H3P03, but this method has the disadvantage that it cannot be carried out on an industrial scale, since tetraphosphorus hexoxide is not a technical product, can only be produced labor-intensive and costly and is generally contaminated with elemental yellow phosphorus.
Die folgenden Beispiele mögen die Einfachheit und den technischen Fortschritt des neuen Verfahrens dokumentieren.The following examples may document the simplicity and technical progress of the new process.
79,6 g (0,4 mol) p-Bromacetophenon werden mit 16,4 g (0,2 mol) phosphoriger Säure in 100 ml Toluol in einem 500-ml-Mehrhalskolben mit Rückflußkühler, Thermometer, Rührer und Tropftrichter vorgelegt und auf 90 - 100°C verwärmt. 27,5 g (0,2 mol) Phosphortrichlorid werden in 30 Minuten unter schwacher Wärmezufuhr zugetropft. Nach 10-minütiger Nachreaktion bei Siedetemperatur wird durch Zugabe von 3,6 g (0,2 mol) Wasser die Pyroverbindung hydrolysiert. Nach abermals 10 Minuten Nachreaktion läßt man abkühlen. Aus der Lösung kristallisiert nach dem Abkühlen 1-(4-Bromphenyl)-vinyl-1-phosphonsäure in farblosen Kristallen aus. 85 g (0,32 mol) der Phosphonsäure werden isoliert, was einer Ausbeute von 80,8 % entspricht. Die Ausbeute kann durch Recirculieren der Mutterlauge weiter gesteigert werden.79.6 g (0.4 mol) of p-bromoacetophenone are initially charged with 16.4 g (0.2 mol) of phosphorous acid in 100 ml of toluene in a 500 ml multi-necked flask equipped with a reflux condenser, thermometer, stirrer and dropping funnel and set to 90 - 100 ° C warmed. 27.5 g (0.2 mol) of phosphorus trichloride are added dropwise in 30 minutes with the application of weak heat. After a 10-minute post-reaction at boiling temperature, the pyro compound is hydrolyzed by adding 3.6 g (0.2 mol) of water. After another 10 minutes of after-reaction, the mixture is allowed to cool. After cooling, 1- (4-bromophenyl) vinyl-1-phosphonic acid crystallizes from the solution in colorless crystals. 85 g (0.32 mol) of the phosphonic acid are isolated, which corresponds to a yield of 80.8%. The yield can be further increased by recirculating the mother liquor.
In einer Apparatur analog Beispiel 1 werden 43,2 g (0,3 mol) α-Tetralon mit 12,1 g (0,15 mol) phosphoriger Säure in 90 ml Toluol vorgelegt und auf 90 - 100°C erwärmt. 20,3 g (0,15 mol) Phosphortrichlorid werden zugetropft. Danach folgt eine Nachreaktion von 30 Minuten bei Siedetemperatur. Nach Abkühlen auf 70°C wird mit 2,7 g (0,15 mol) Wasser hydrolysiert. Nach dem Abkühlen lassen sich 56 g (0,27 mol) 3,4-Dihydro- naphthalin-1-phosphonsäure isolieren, was einer Ausbeute von 90 % entspricht. Durch Recirculieren der Mutterlauge läßt sich die Ausbeute auf über 90 % steigern.43.2 g (0.3 mol) of α-tetralone with 12.1 g (0.15 mol) of phosphorous acid in 90 ml of toluene are placed in an apparatus analogous to Example 1 and heated to 90-100.degree. 20.3 g (0.15 mol) of phosphorus trichloride are added dropwise. This is followed by an after-reaction of 30 minutes at boiling temperature. After cooling to 70 ° C is hydrolyzed with 2.7 g (0.15 mol) of water. After cooling, 56 g (0.27 mol) of 3,4-dihydronaphthalene-1-phosphonic acid can be isolated, which corresponds to a yield of 90%. By recirculating the mother liquor, the yield can be increased to over 90%.
In einer Apparatur analog Beispiel 1 werden 80,4 g (0,67 mol) Acetophenon mit 27,5 g (0,335 mol) phosphoriger Säure in 100 ml Methylenchlorid vorgelegt und zum Sieden erhitzt.80.4 g (0.67 mol) of acetophenone with 27.5 g (0.335 mol) of phosphorous acid in 100 ml of methylene chloride are placed in an apparatus analogous to Example 1 and heated to boiling.
46,1 g (0,335 mol) Phosphortrichlorid werden in 50 Minuten zudosiert. 6,2 g (0,34 mol) Wasser werden zugesetzt, das Lösemittel abdestilliert und der Rückstand 10 Minuten auf 150°C erhitzt. 120 g Rohprodukt werden isoliert mit einer Zusammensetzung laut 31P-NMR-Spektrum von 91,2 Gew% 1-Phenyl- vinyl-1-phosphonsäure, 1,9 Gew% 1-Hydroxy-1-phenylvinyl-1-phosphonsäure, 5,1 Gew% phosphoriger Säure und 1,8 Gew% Phosphorsäure.46.1 g (0.335 mol) of phosphorus trichloride are metered in in 50 minutes. 6.2 g (0.34 mol) of water are added, the solvent is distilled off and the residue is heated to 150 ° C. for 10 minutes. 120 g of crude product are isolated with a composition according to the 31 P-NMR spectrum of 91.2% by weight of 1-phenyl-vinyl-1-phosphonic acid, 1.9% by weight of 1-hydroxy-1-phenylvinyl-1-phosphonic acid, 5. 1% by weight of phosphorous acid and 1.8% by weight of phosphoric acid.
In einer Apparatur analog Beispiel 1 werden 184 g (1,53 mol) Acetophenon zusammen mit 41,4 g (2,3 mol) Wasser vorgelegt und auf 80°C erwärmt. 210,8 g (1,53 mol) Phosphortrichlorid werden zugetropft, wobei die Reaktionstemperatur gegen Ende des Zutropfens auf 100°C gesteigert wird. Das Produkt wird mit 13,9 g (0,77 mol) Wasser hydrolysiert und 5 Minuten auf 150°C erhitzt. Es werden 279 g Reaktionsprodukt isoliert mit einer Zusammensetzung laut 31P-NMR-Spektrum von 87% 1-Phenyl- vinyl-1-phosphonsäure neben u.a. 4 % phosphoriger Säure.184 g (1.53 mol) of acetophenone together with 41.4 g (2.3 mol) of water are placed in an apparatus analogous to Example 1 and heated to 80.degree. 210.8 g (1.53 mol) of phosphorus trichloride are added dropwise, the reaction temperature being raised to 100 ° C. towards the end of the dropwise addition. The product is hydrolyzed with 13.9 g (0.77 mol) of water and heated to 150 ° C. for 5 minutes. 279 g of reaction product are isolated with a composition according to the 31 P-NMR spectrum of 87% 1-phenyl-vinyl-1-phosphonic acid in addition to, inter alia, 4% phosphorous acid.
In einer Apparatur analog Beispiel 1 werden 144 g (1,2 mol) Acetophenon zusammen mit 137,5 g (1 mol) Phosphortrichlorid vorgelegt. Bei Raumtemperatur beginnt man mit der Wasserdosierung. 27 g (1,5 mol) Wasser werden innerhalb von 35 Minuten zugesetzt, wobei die Reaktionstemperatur bei geringer Wärmezufuhr gegen Ende 100°C erreicht. Im Wasserstrahlvakuum wird bei 150°C überschüssiges Keton abgezogen. Die so erhaltenen 141 g Rohprodukt werden mit 80 ml Wasser hydrolysiert und zu 221 g wäßriger Produktlösung verdünnt. Als Zusammensetzung ergibt sich nach dem 31P-NMR-Spektrum (bezogen auf wasserfreies Endprodukt) : ca. 95 Gew% 1-Phenylvinyl-1-phosphonsäure neben u.a. ca. 1,4 Gew% Phosphorsäure und ca. 1,2 Gew% phosphoriger Säure.144 g (1.2 mol) of acetophenone together with 137.5 g (1 mol) of phosphorus trichloride are placed in an apparatus analogous to Example 1. At room temperature you start water metering. 27 g (1.5 mol) of water are added over the course of 35 minutes, the reaction temperature reaching 100 ° C. towards the end with little heat. Excess ketone is drawn off at 150 ° C. in a water jet vacuum. The 141 g of crude product thus obtained are hydrolyzed with 80 ml of water and diluted to 221 g of aqueous product solution. The 31 P-NMR spectrum (based on anhydrous end product): approx. 95% by weight of 1-phenylvinyl-1-phosphonic acid in addition to, inter alia, approx. 1.4% by weight of phosphoric acid and approx. 1.2% by weight of phosphorous acid.
In einer Apparatur analog Beispiel 1 werden 49 g (0,5 mol) Cyclohexanon mit 20,5 g (0,25 mol) phosphoriger Säure in 100 ml Toluol vorgelegt und auf 90°C erwärmt. 34 g (0,25 mol) Phosphortrichlorid in 50 ml Toluol werden zugetropft. Das Lösemittel wird anschließend abdestilliert und das Rohprodukt für 2 Minuten auf 200°C erhitzt. Nach dem Abkühlen auf 100°C wird mit 4,5 g (0,25 mol) Wasser hydrolysiert und das Rohprodukt in Eisessig aufgenommen. Aus der essigsauren Lösung kristallisieren 50 g (0,3 mol) Cyclohexen-1-phosphonsäure aus, was einer Ausbeute von 61,7 % entspricht.49 g (0.5 mol) of cyclohexanone with 20.5 g (0.25 mol) of phosphorous acid in 100 ml of toluene are placed in an apparatus analogous to Example 1 and heated to 90.degree. 34 g (0.25 mol) of phosphorus trichloride in 50 ml of toluene are added dropwise. The solvent is then distilled off and the crude product is heated to 200 ° C. for 2 minutes. After cooling to 100 ° C., 4.5 g (0.25 mol) of water are hydrolyzed and the crude product is taken up in glacial acetic acid. 50 g (0.3 mol) of cyclohexene-1-phosphonic acid crystallize out of the acetic acid solution, which corresponds to a yield of 61.7%.
In einer Apparatur analog Beispiel 1 werden 300 ml Aceton mit 27 g (1,5 mol) Wasser vorgelegt und zum Sieden erhitzt. 137,5 g (1 mol) Phosphortrichlorid werden zugetropft. Nach 10 Minuten Nachreaktion bei Siedetemperatur wird mit 20 ml Wasser hydrolysiert; die Lösungsmittelphase wird von dem entstandenen Harz abgetrennt, welches anschließend 2 Minuten auf 200°C erhitzt wird. Es werden 92 g Produkt mit einer Zusammensetzung laut 31P-NMR-Spektrum von 75 Gew% Propen-2-phosphonsäure neben 25 Gew% phosphoriger Säure erhalten.300 ml of acetone with 27 g (1.5 mol) of water are placed in an apparatus analogous to Example 1 and heated to boiling. 137.5 g (1 mol) of phosphorus trichloride are added dropwise. After 10 minutes of subsequent reaction at boiling temperature, hydrolysis is carried out with 20 ml of water; the solvent phase is separated from the resulting resin, which is then heated to 200 ° C. for 2 minutes. 92 g of product with a composition according to the 31 P-NMR spectrum of 75% by weight propene-2-phosphonic acid in addition to 25% by weight phosphorous acid are obtained.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833323392 DE3323392A1 (en) | 1983-06-29 | 1983-06-29 | METHOD FOR PRODUCING DERIVATIVES OF VINYLPHOSPHONIC OR VINYLPYROPHOSPHONIC ACIDS |
| DE3323392 | 1983-06-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0130439A1 true EP0130439A1 (en) | 1985-01-09 |
| EP0130439B1 EP0130439B1 (en) | 1987-04-15 |
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ID=6202667
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84106863A Expired EP0130439B1 (en) | 1983-06-29 | 1984-06-15 | Process for the preparation of vinylphosphonic acid or vinylpyrophonic acid |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4529559A (en) |
| EP (1) | EP0130439B1 (en) |
| JP (1) | JPS6023389A (en) |
| DD (1) | DD220605A5 (en) |
| DE (2) | DE3323392A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0205820A1 (en) * | 1985-05-18 | 1986-12-30 | Hoechst Aktiengesellschaft | Carboxytetralinphosphonic acids and process for their preparation |
| WO1998050390A1 (en) * | 1997-05-02 | 1998-11-12 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391816A (en) * | 1993-11-08 | 1995-02-21 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
| WO1996024599A1 (en) | 1995-02-10 | 1996-08-15 | Akzo Nobel N.V. | Synthesis of a hydrocarbylvinyl phosphonic acid hydrocarbyl ester |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2060218A1 (en) * | 1970-12-08 | 1972-06-15 | Knapsack Ag | Process for the preparation of 1-phenyl-vinyl-1-phosphonic acid |
| DE2060259A1 (en) * | 1970-12-08 | 1972-06-15 | Knapsack Ag | Phenyl-vinyl-phosphonic acids and processes for their production |
| EP0068350A1 (en) * | 1981-06-27 | 1983-01-05 | Hoechst Aktiengesellschaft | Process for preparing derivatives of vinyl phosphonic or vinyl pyrophosphonic acids |
| GB2102427A (en) * | 1981-08-01 | 1983-02-02 | Roehm Gmbh | Substituted phosphonic acids |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2254124A (en) * | 1939-06-05 | 1941-08-26 | Du Pont | Organic compound of quinquevalent phosphorus |
| US2694684A (en) * | 1951-12-11 | 1954-11-16 | Standard Oil Dev Co | Lubricating oil compositions |
| SU899565A1 (en) * | 1980-03-21 | 1982-01-23 | Ордена Ленина Институт Элементоорганических Соединений Ан Ссср | Process for producing alpha-hydroxyphosphine acids |
-
1983
- 1983-06-29 DE DE19833323392 patent/DE3323392A1/en not_active Withdrawn
-
1984
- 1984-06-15 DE DE8484106863T patent/DE3463144D1/en not_active Expired
- 1984-06-15 EP EP84106863A patent/EP0130439B1/en not_active Expired
- 1984-06-15 US US06/620,940 patent/US4529559A/en not_active Expired - Fee Related
- 1984-06-27 JP JP59131219A patent/JPS6023389A/en active Granted
- 1984-06-27 DD DD84264589A patent/DD220605A5/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2060218A1 (en) * | 1970-12-08 | 1972-06-15 | Knapsack Ag | Process for the preparation of 1-phenyl-vinyl-1-phosphonic acid |
| DE2060259A1 (en) * | 1970-12-08 | 1972-06-15 | Knapsack Ag | Phenyl-vinyl-phosphonic acids and processes for their production |
| EP0068350A1 (en) * | 1981-06-27 | 1983-01-05 | Hoechst Aktiengesellschaft | Process for preparing derivatives of vinyl phosphonic or vinyl pyrophosphonic acids |
| GB2102427A (en) * | 1981-08-01 | 1983-02-02 | Roehm Gmbh | Substituted phosphonic acids |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0205820A1 (en) * | 1985-05-18 | 1986-12-30 | Hoechst Aktiengesellschaft | Carboxytetralinphosphonic acids and process for their preparation |
| WO1998050390A1 (en) * | 1997-05-02 | 1998-11-12 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0421677B2 (en) | 1992-04-13 |
| JPS6023389A (en) | 1985-02-05 |
| DD220605A5 (en) | 1985-04-03 |
| EP0130439B1 (en) | 1987-04-15 |
| DE3323392A1 (en) | 1985-01-10 |
| US4529559A (en) | 1985-07-16 |
| DE3463144D1 (en) | 1987-05-21 |
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